Textile product and method of making the same



'jPatented July 21, .1936 I.

2,048,248 onucr AND Ms'rnon or IF THE S Camille Dreyfus, Ncvv'York, N. Y., and George Schneider, Montclair, N. .J., assignors to Celanese Corporation of America, a corporation of Dela No Drawing. Application August t as (or. 10640) This invention relates to a method of preparing artificial filamentsyarns and other textile materials.

An object of our invention is to prepare artificial filaments having their appearance or other properties modified by the incorporation therein of finely divided solids. A further object of our invention is to prepare such solids in a state of minute subdivision. Other objects of this invention will appear from the following detailed description. s

It has been previously proposed to incorporate white inorganic pigment-like material in spinning solutions in order to produce artificial yarns of subdued lustre and increased opacity. In commercial processes involving the use of such pigments, it was necessary to subject the pigments to prolonged and elaborate grinding processes in order to attain the degree of subdivision necessary to prevent clogging of the fine orifices of the spinning jets and to avoid reducing the strength of the resulting filaments to an undue extent. However, even after such prolonged grinding, the size of the pigment particles is not reduced to as great a degree as is often desired.

Furthermore, it has been previously proposed to incorporate colored pigments in spinning solutions in order to produce colored yarn. However,

despite the great care taken in grinding such colcred pigments, the tinctorial value of the same is relatively low so that relatively large amounts thereof must be employed, and even the use of such large amounts does not'produce the desired depth of shade. A

We have found that if pigments or other solid materials are prepared by subjecting them to squeezing, rubbing or kneading action while they are dispersed'in a plastic mass, which mass .preferably comprises a derivative of cellulose, they 40 are reduced in a relatively short time to such a fine state of subdivision as is not attainable by prior methods. Not only is the timeol treatment reduced, but the particles 01 solids may be used in smaller quantities to obtain eitects such as reduction of lustre or depth of colorations heretofore unattainable.

in accordance with our invention then we prepare artificial filaments containing celluloslctma- 5o terial by incorporating in a spinning solution irom which they are formed a finely divided pigment or other insoluble solid which has been preparedby subiectingthesametoasqueezing, rub-. bingorkneadingactionwhiledispeisedinam 64 ticmasswhichpreterablycompriscsthesamecellulosic compound lution.

The filaments made in accordance with this invention may be of fine denier which are associ ated together by twisting to form yarn, or the filaments may be heavier, such as bristles, artificial horsehair and straw. Such filaments may be made by the viscose, cuprammonium, Chardonnet or other process, but this invention is of particular importance in connection with filaments made of organic derivatives of cellulose such as organic esters or cellulose and cellulose ethers'. Examples of organic esters of cellulose are cellulose acetate, cellulose iormate, cellulose. propionate and cellulose butyrate, while examples of cellulose ethers 15 are ethyl cellulose, methyl cellulose and benzyl cellulose. The filaments containing the organic derivative of cellulose may be prepared by dissolve ing the organic derivative of cellulose in a volatile solvent such as acetone and extruding such 20 solutions through fine orifices into an evaporative atmosphere, as in-dry spinning, or into a precipitating bath, as in wet spinning. I

As stated, we add a. finely divided pigment or solid modifying agentto thespinning solution or 25 dope. This pigment may be white to,obtaln sub-' dued lustre and increased opacity. Examples of white inorganic pigments are tin oxide, tin phosphate, antimony oxide, titanium dioxide, barium sulfate, lead sulfate, calcium sulfate, zinc oxide, 30 zinc carbonate, aluminum oxide, silicon dioxide, barium borate, calcium borate or silicates such as china clay or other clays, talc or mica. The pigment may be of organic nature sucn as diacetyl benzidine, diacetyl toluidine, dlbenzoyl benzidine, naphthyl. urea, anthraquinone, anthracene, suitable synthetic or natural resins, cellulose in the form of fibres or powder, degraded I cellulose, starches etc.

contained in the spinning so- This invention is of particular interest for the preparation of colored filaments, in which case a colored inorganic or organic pigment may be employed to obtain the desired color or shade. For a yellow color, ochre, sienna, chrome yellow. tin bronze, etc. may be employed. For a red color, Venetian red, red lead, vermillion, etc., may

be employed. For a blue ,color, ultramarine,

- Prussian blue, Milori blue, etc., may be used./ For green, Guignets green, verdigrls, chrome {green may be employed. For brown, raw umber, bumtumber or Vandyke brown may be used. For black, lamp black, carbon black. r phite or other black pigment may be used,-which may be toned with iron gallate or other toners to obtain let blacks. To obtain any other colors,

in the paint art. To obtain metallic efiects, finely divided or colloidal metals may be employed.

The amount of pigment added will vary with a degree of subdued lustre and/or the depth of color desired and the nature of thepigment employed and will generally be from,0.1 to of "the weight of the cellulosic material present in ments.

Other solid modifying agents that are insoluble or incompatible with both the solvent and the derivative of cellulose'present in the spinning solution may likewise be incorporated in accordance with our invention.

As stated, prior toincorporation in the spinning solution, the pigment or like material is reduced to a very fine state of subdivision by subjecting it to a manipulation involving kneading, squeezing or rubbing operations while dispersed in a plastic This action causes the breaking up or disintegration of the agglomerates or aggregates in which the pigment particles may occur. These operations are conveniently carried out by processes ordinarily, employed for making articles from cellulose derivative plastics. Thus a heavysolution or plastic mass may be formed by mixing the same derivative of cellutially all ofthe volatile'liquid is evaporated.

The sheets are finally broken into pieces which are then used for incorporation in the spinning solution.

This kneading, rubbing or squeezing operation reduces the pigments to extremely fine particle size which is usually less tban'one micron in diameter. As an example of the minuteness ofsbbdivision attainable by this method, it is pointed out that if carbon black is treated, substantialiy all, or at least a major portion of the particles are too small to measuremicroscopically having a diameter less than 0.2 micron,

there being present about 10% of aggregates Q having diameters of between 0.2 to 0.5 micron.

Because of theminute size of the particles,'. filaments containing them have substantially the same tenacity and elongation as filaments free 1 of any. pi ments, while the incorporation of pigments ground by prior methods appreciably reduces the tenacity and elongation. The filaments prepared in accordance with this invention have a greater depth of color and/or subdued lustre than'filaments containing appreciably larger amounts of pigments previously employed. By way of example, it is pointed out that whereas=it is possible to obtain only a grey-black by cific example is given.

2,048,248 thepigments maybemixedasiswell understood.

incorporating any amount of carbon blackby the previous method, a jet black may be obtained by the incorporation in a spinning solution of but a very small quantity of carbon black prepared in accordance with this invention. In order further to illustrate, our invention but without being limited thereto, the following spe- Example The. following-ingredients: Y

Part by weight Cellulose acetate 1 Carbon black 1 Acetone 1.5

are kneaded together in a heated kneading machine until a still doughy mass is formed. This mass is then worked between relatively closely spaced heated malaxating rolls until the product is substantially free of the acetone which is a volatile solvent for the cellulose acetate. The resulting sheet is broken'into chips or pieces.

A spinning solution is formed bydissolving one part by weight of cellulose acetate in three parts by weight'of acetone and to this is added an amount of above described pieces or chips so that the'solution contains 0.03 part of carbon black. The ingredients are thoroughly mixed and are thenfiltered, and the filtered spinning solution is extruded through the fine orifices of a spinning jet into a heated evaporative atmos-. phere. The resulting filaments are twisted and wound onto a package.

The yarn so formed is jet black, and maybe used for weaving or knitting fabrics that are as black as any cellulose acetate fabric that has been dyed in the piece.

. It is to be understood that the foregoing detailed description is given merely by way of illustration and many variations may be made therein without departing from the spirit of our invention. s

Having described our invention, what we desire to secure byLetters Patent is:- s

1. In a process for the manufacture ofartificial filaments, yarns and the like from solutions of derivatives of cellulose by wet or dry spinning processes, the steps of working a plastic mass comprising a derivative of cellulose and a pigmentlike material between rolls until the plasticmass is brought to a substantially dry state and the particle size of the pigment-like material is reduced, and dispersing pieces of the resulting product in the spinning solution cellulose derivative.

2. In a process for the manufacture of artificial filaments, yarns and the like from solutions of cellulose acetate by wet or dry spinning processes,

-filaments, yarns and the like from solutions of V cellulose acetate by wetordry spinning processes, 70

the steps of working ta; plastic mass comprising cellulogyaoetate, a softeningi'gent therefor, and carbon blak between rolls until the plastic mass is brought to a su'bstantiallydry state and the containing thewsame particle size of carbon black is reducedto below 7 0.5 microns, and dispersing the pieces of the resame cellulose derivative and the pigment-like suiting product in the spinning solution. -material between rolls until the plastic mass is 4. Artificial filaments comprising a cellulose brought to a substantially dry state and the derivative and finely divided pigment-like mateparticle size of the pigment-like material is re- 5 rial produced from a spinning solution of a celluduced.

lose derivative in which has been dispersed pieces CAMJILE DREYFUS. formed by working a plastic mass comprising the GEORGE SCHNEIDER. 

